JPS62280263A - Cyanine dye - Google Patents
Cyanine dyeInfo
- Publication number
- JPS62280263A JPS62280263A JP61125110A JP12511086A JPS62280263A JP S62280263 A JPS62280263 A JP S62280263A JP 61125110 A JP61125110 A JP 61125110A JP 12511086 A JP12511086 A JP 12511086A JP S62280263 A JPS62280263 A JP S62280263A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- ethyl
- cyanine dye
- verchlorate
- propyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 title claims abstract 3
- 150000001450 anions Chemical group 0.000 claims abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000975 dye Substances 0.000 abstract description 32
- 239000000463 material Substances 0.000 abstract description 10
- 150000003839 salts Chemical class 0.000 abstract description 6
- 230000001235 sensitizing effect Effects 0.000 abstract description 5
- KBHPJZNRPYBVNO-UHFFFAOYSA-N 5-anilinopenta-2,4-dienyl(phenyl)azanium;chloride Chemical compound Cl.C=1C=CC=CC=1NC=CC=CCNC1=CC=CC=C1 KBHPJZNRPYBVNO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 13
- 235000017281 sodium acetate Nutrition 0.000 description 13
- 239000001632 sodium acetate Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 108091008695 photoreceptors Proteins 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 description 1
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 1
- XXNOGQJZAOXWAQ-UHFFFAOYSA-N 4-chlorophenylhydrazine Chemical class NNC1=CC=C(Cl)C=C1 XXNOGQJZAOXWAQ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- -1 tetrafluoroborate Chemical compound 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
- G11B7/247—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes methine or polymethine dyes
- G11B7/2472—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes methine or polymethine dyes cyanine
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、近赤外領域に極大吸収波長を有する新規なシ
アニン色素に関し、さらに詳しくは、レーザービームに
より直接記録し、反射光の変化によって情報再生を行な
う光学的情報記録媒体の材料として特に有用な色素に関
する。Detailed Description of the Invention [Technical Field] The present invention relates to a novel cyanine dye having a maximum absorption wavelength in the near-infrared region. The present invention relates to dyes that are particularly useful as materials for optical information recording media.
従来より、シアニン色素の薄膜を記録層として適用した
光学的情報記録媒体は知られている（例えば、特開昭５
９−８５７９Ｌ号公報）。このシアニン色素を用いる記
録媒体は、その吸光係数が、他の近赤外領域に吸収を示
す色素に比較して特に大きな値をもつため、感度（記録
再生）およびＳ／Ｎが高く、しかも保存性の高い光学的
情報記録媒体である。Optical information recording media to which a thin film of cyanine dye is applied as a recording layer have been known (for example, in Japanese Patent Application Laid-Open No.
9-8579L). Recording media using this cyanine dye have a particularly large extinction coefficient compared to other dyes that absorb in the near-infrared region, so they have high sensitivity (recording/reproduction) and S/N, and they also have high storage capacity. It is a highly flexible optical information recording medium.
また、この記録媒体は、基本的には基鈑上にシアニン色
素を含む薄膜を蒸着、塗布などの種々の方法を用いて形
成することができ、とりわけ塗布による薄膜形成は他の
方法に比較して工業的に有利な方法であるといえるが、
シアニン色素を有機溶剤に溶解させて溶液とする工程を
必要とする。しかしながら、従来公知のシアニン色素は
有機溶剤に対する溶解性が低く、また安定性に欠けろた
め溶解工程におけるシアニン色素の分散性及び安定性が
悪くなり、これを塗布した記録媒体は記録の再生性ある
いは保存性が不充分なものであった。In addition, this recording medium can basically be formed by using various methods such as vapor deposition and coating to form a thin film containing cyanine dye on a substrate. It can be said that it is an industrially advantageous method, but
It requires a step of dissolving the cyanine dye in an organic solvent to form a solution. However, conventionally known cyanine dyes have low solubility in organic solvents and lack stability, resulting in poor dispersibility and stability of the cyanine dyes in the dissolution process, and recording media coated with these have poor recording reproducibility. The shelf life was insufficient.
本発明は、近赤外領域に極大吸収波長を有すると共に化
学的安定性及び各種有機溶剤への溶解性に優れた新規な
シアニン色素を提供することを目的とする。An object of the present invention is to provide a novel cyanine dye that has a maximum absorption wavelength in the near-infrared region and has excellent chemical stability and solubility in various organic solvents.
本発明に°よれば、一般式（１）
％式％
（式中、Ｒｏ、Ｒ２は水素原子又は塩素原子を表わし、
Ｒ１とＲ４はメチル基、エチル基、又はプロピル基を表
わし、Ｘ−は酸陰イオンを表わす。但しＲ１とＲ２が等
しく、かつＲ３とＲ４が等しい場合は除く。）
で表わされるシアニン色素が提供される。According to the present invention, general formula (1) % formula % (wherein Ro and R2 represent a hydrogen atom or a chlorine atom,
R1 and R4 represent a methyl group, an ethyl group, or a propyl group, and X- represents an acid anion. However, the case where R1 and R2 are equal and R3 and R4 are equal is excluded. ) A cyanine dye is provided.
上記一般式（Ｉ）における酸陰イオンとしては、ハロゲ
ン、アルキル硫酸塩、アリールスルホニル基、バークロ
レート、テトラフルオロボレート等が挙げられる。Examples of the acid anion in the above general formula (I) include halogen, alkyl sulfate, arylsulfonyl group, verchlorate, and tetrafluoroborate.
本発明の前記一般式（１）で示されるシアニン色素は、
近赤外領域に極大波長吸収を有するものであり、また化
学的に安定な物質である上、メタノール、エタノール、
イソプロパツールなどのアルコール類、アセトン、メチ
ルエチルケトン、シクロヘキサノンなどのケトン類、エ
チルエーテル、ジオキサン、テトラヒドロフランなどの
エーテル類、酢酸エチル、酢酸ｎ−ブチルなどのエステ
ル類、更にクロロホルム、１，２−ジクロルエタン、ジ
メチルホルムアミドなどの各種有機溶剤及びこれらの混
合溶媒に溶解する。The cyanine dye represented by the general formula (1) of the present invention is:
It has maximum wavelength absorption in the near-infrared region, and is a chemically stable substance, as well as methanol, ethanol,
Alcohols such as isopropanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethers such as ethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate and n-butyl acetate; and chloroform, 1,2-dichloroethane, Soluble in various organic solvents such as dimethylformamide and mixed solvents thereof.
したがって、本発明のシアニン色素は、レーザービーム
による記録再生用媒体として使用できる利点を有するほ
か、複写及び印刷用の感光体、または感光体の増感色素
として、また、銀塩写真の増感色素として利用でき、更
に光学フィルター、ディスプレー材料、塗料などの材料
としても有効に利用できる。Therefore, the cyanine dye of the present invention has the advantage that it can be used as a recording and reproducing medium using a laser beam, and can also be used as a sensitizing dye for photoreceptors or photoreceptors for copying and printing, and as a sensitizing dye for silver salt photography. It can also be used effectively as a material for optical filters, display materials, paints, etc.
本発明のシアニン色素は、従来この分野で知られている
各種の製造法を応用することによって合成することがで
きるが１本発明のシアニン色素は、左右のインドレニン
の構造が異なった非対称型の色素であるので、２工程の
反応で合成する。第１工程は、下式に示すように一般式
（■）で示されるインドレニウム塩誘導体と１−７ニリ
ノー５−アニリノペンタ−１，３−ジエン塩酸塩を等モ
ル比で反応させて、一般式（ｍ）で示される中間体を合
成する。The cyanine dye of the present invention can be synthesized by applying various production methods conventionally known in this field.1 The cyanine dye of the present invention is an asymmetric type in which the structures of the left and right indolenines are different. Since it is a pigment, it is synthesized in a two-step reaction. The first step is to react an indolenium salt derivative represented by the general formula (■) and 1-7nilino-5-anilinopenta-1,3-diene hydrochloride in an equimolar ratio as shown in the following formula, and Synthesize the intermediate shown in (m).
’７１１）
バ３
（ｍ）
第２工程は、次の反応式に示され、第１工程で合成した
中間体（［）と一般式（ＩＶ）で示されるインドレニウ
ム塩誘導体を等モル比で反応させて、本発明の一般式（
Ｉ）で示されるシアニン色素を製造する。'711) Ba3 (m) The second step is shown in the following reaction formula, and the intermediate ([) synthesized in the first step and the indolenium salt derivative shown by the general formula (IV) are mixed in an equimolar ratio. The general formula of the present invention (
A cyanine dye represented by I) is produced.
（ＩＩＩ）
（ＩＶ）（式中、Ｒ□とＲ２は水素原子又は塩
素原子を表わし、Ｒ１とＲ４はメチル基、エチル鋸又は
プロピル、基を表わし、Ｘ−は酸陰イオンを表わす。但
し、Ｒ工とＲ２が等しく、かつＲ１とＲ４が等しい場合
は除く。）
上記二工程は共に、反応溶媒として無水酢酸、アルコー
ル類を使用して７０〜１２０℃で０．５〜５．０時間反
応させる。また、溶媒が無水酢酸のときは、酢酸ナトリ
ウムを、またアルコール類のときは、酢酸ナトリウム又
は第３級アミン、例えば、トリエチルアミン、ピペラジ
ンなどの弱塩基を加えることにより、反応速度を促進す
ることができる。(III)
(IV) (In the formula, R□ and R2 represent a hydrogen atom or a chlorine atom, R1 and R4 represent a methyl group, an ethyl group, or a propyl group, and X- represents an acid anion. However, R (Except when R2 is equal and R1 and R4 are equal.) Both of the above two steps are reacted at 70 to 120°C for 0.5 to 5.0 hours using acetic anhydride and alcohols as reaction solvents. When the solvent is acetic anhydride, the reaction rate can be accelerated by adding sodium acetate, and when the solvent is an alcohol, adding sodium acetate or a weak base such as a tertiary amine such as triethylamine or piperazine. can.
原料のインドレニウム塩誘導体は、例えば、下記に記述
するような方法で合成することができる。The raw material indolenium salt derivative can be synthesized, for example, by the method described below.
フェニルヒドラジン又は４−クロロフェニルヒドラジン
誘導体の塩酸塩と３−メチル−２−ブタノンをエタノー
ル溶媒中、硫酸酸性下で煮沸還流させて、２，３，３．
− トリメチルインドレニン誘導体を合成する。次に該
誘導体とジアルキル硫酸又はハロゲン化アルキルとを５
０〜１２０℃で０．５〜５．０時間反応させることによ
り、１−アルキル−２，３，３−トリメチルインドレニ
ウム塩誘導体を合成することができる。Hydrochloride of phenylhydrazine or 4-chlorophenylhydrazine derivative and 3-methyl-2-butanone are boiled and refluxed in an ethanol solvent under acidic sulfuric acid to produce 2,3,3.
- Synthesize trimethylindolenine derivatives. Next, the derivative and dialkyl sulfate or alkyl halide are combined into 5
A 1-alkyl-2,3,3-trimethylindolenium salt derivative can be synthesized by reacting at 0 to 120°C for 0.5 to 5.0 hours.
また、１−アニリノ−５−アニリノペンタ−１，３−ジ
エン塩酸塩は１尾形等の文献（Ｂｕｌｌ、Ｉｎ５ｔ。In addition, 1-anilino-5-anilinopenta-1,3-diene hydrochloride is a one-tailed form (Bull, In5t).
Ｐｈｙｓ、Ｃｈｅｍ、Ｒｅｓ、 （Ｔｏｋｙｏ） 、
１３．Ｐ５１１． （１９３４）を参照）の実験例を参
考にして合成することができる。Phys, Chem, Res, (Tokyo),
13. P511. (1934)).
本発明のシアニン色素を使用して光学的情報記録媒体を
作成するには、シアニン色素を上記溶剤または混合溶剤
に溶解し、その溶液を基板上に塗布して、シアニン色素
を含む薄膜を形成する。基鈑材料の材質としては、ガラ
ス、石英、セラミック、プラスチック、紙、板状または
箔状の金属などの一般に使用されている記録材料の支持
体でよい。また、塗布の方法としては、スプレー、ロー
ラーコーティング、ディッピングおよびスピニングなど
の慣用のコーティング方法を用いることができる。To create an optical information recording medium using the cyanine dye of the present invention, the cyanine dye is dissolved in the above solvent or mixed solvent, and the solution is applied onto a substrate to form a thin film containing the cyanine dye. . The substrate material may be a commonly used recording material support such as glass, quartz, ceramic, plastic, paper, plate-shaped or foil-shaped metal. Moreover, as a method of application, conventional coating methods such as spraying, roller coating, dipping, and spinning can be used.
本発明で得られる前記一般式（１）で示されろ新規なシ
アニン色素は、近赤外領域に極大波長を有すると共に化
学的安定性及び各種有機溶剤への溶解性に優れたもので
ある。The novel cyanine dye represented by the general formula (1) obtained by the present invention has a maximum wavelength in the near-infrared region and has excellent chemical stability and solubility in various organic solvents.
したがって、本発明のシアニン色素は、レーザービーム
による記録再生用媒体として使用できる利点を有するほ
か、複写及び印刷用の感光体、または感光体の増感色素
として、また銀塩写真の増感色素として利用でき、更に
光学フィルター、ディスプレー材料、塗料などの材料と
しても有効に利用できるものである。Therefore, the cyanine dye of the present invention has the advantage that it can be used as a recording and reproducing medium using a laser beam, and also as a sensitizing dye for photoreceptors or photoreceptors for copying and printing, and as a sensitizing dye for silver salt photography. Furthermore, it can be effectively used as a material for optical filters, display materials, paints, etc.
以下、実施例により本発明の詳細な説明する。 Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例１
（１，３，３−トリメチル−５−クロロインド−１′−
エチル−３ｒ、３ｔ−ジメチルインド−２：２′−へブ
タメチンシアニンパーグロレート
の製造〕
原料の１つである２−（６’ −アセトアニリノヘキサ
−１’、３’、５’ −トリエニル）−１，３，３−ト
リメチル−５−クロロインドレニウムバークロレートＣ
Ｈ。Example 1 (1,3,3-trimethyl-5-chloroindo-1'-
Production of ethyl-3r,3t-dimethylindo-2:2'-hebutamethine cyanine perglolate] 2-(6'-acetanilinohexa-1',3',5'- trienyl)-1,3,3-trimethyl-5-chloroindolenium verchlorate C
H.
は次のように合成した。was synthesized as follows.
１．２，３．３−テトラメチル−５−クロロインドレニ
ウムバークロレート２９．６ｇ、１−アニリノ−５−ア
ニリノペンタ−１，３−ジエン塩酸塩（融点１３７〜１
３９’Ｃ）２９．６ｇ、酢酸ナトリウム８．２ｇと無水
酢酸２５０ｃｃを９０〜１００℃で１時間反応させた。1.2,3.3-tetramethyl-5-chloroindolenium verchlorate 29.6 g, 1-anilino-5-anilinopenta-1,3-diene hydrochloride (melting point 137-1
39'C), 8.2 g of sodium acetate, and 250 cc of acetic anhydride were reacted at 90 to 100°C for 1 hour.
冷却後、析出した結果を濾取し結晶を水洗後、メタノー
ル、クロロホルム又はアセトンで数回洗浄した。収ｉ１
ｇ、３島融点１６３〜１６５℃。After cooling, the precipitated result was collected by filtration, and the crystals were washed with water and then several times with methanol, chloroform, or acetone. Collection i1
g, 3-island melting point 163-165°C.
上記で得た２−（６’ −アセトアニリノヘキサ−１′
、３′、５′ −トリエニル）−１，３，３−トリメチ
ル−５−クロロインドレニウムバークロレート４．６ｇ
、■−エチルー２．３．３− トリメチルインドレニウ
ムバークロレート（融点２０９〜２１１°Ｃ）２．９ｇ
、酢酸ナトリウム０．８２ｇとｎ−ブタノール５０ｃｃ
を９０〜１００℃で１．５時間反応させた。冷却後、析
出した結晶をメタノ−ルで数回再結晶した。収′Ｂｋ３
、４ ｇ、融点２０９〜２１０℃、エタノール中の極
太吸収波長７４８ｎｍ。2-(6'-acetanilinohexa-1' obtained above)
, 3',5'-trienyl)-1,3,3-trimethyl-5-chloroindolenium verchlorate 4.6 g
, ■-Ethyl-2.3.3-trimethylindolenium verchlorate (melting point 209-211°C) 2.9g
, sodium acetate 0.82g and n-butanol 50cc
was reacted at 90 to 100°C for 1.5 hours. After cooling, the precipitated crystals were recrystallized several times from methanol. Collection'Bk3
, 4 g, melting point 209-210°C, thick absorption wavelength 748 nm in ethanol.
実施例２
（１，３，３−トリメチル−５−クロロインド−１１−
エチル−３’ 、３’ −ジメチル−５′−クロロイン
ド−２：２’ −へブタメチンシアニンバークロレート
の製造〕
実施例１で得た２−（６’ −アセトアニリノヘキサ−
１’、３’、５’ −トリエニル）−１，３，３−トリ
メチル−５−クロロインドレニウムバークロレート４．
６ｇ、１−エチル−２，３，３−トリメチル−５−クロ
ロインドレニウムエチルスルホネート（ｗＡ点１６５〜
１６６℃）３．２ｇ、酢酸ナトリウム０．８２ｇとｎ−
ブタノール５０ｃｃを９０〜１００℃で１．５時間反応
させた。冷却後、析出した結晶を濾取し、熱メタノール
で洗浄した。収量３．０７ｇ、融点２２５〜２２６℃、
エタノール中の極大吸収波長７５２０ｍ０
実施例３
（１，３，３−トリメチル−５−クロロインド−１′−
プロピル−３’、３’ −ジメチルインド−２＝２′
−へブタメチンシアニンバークロレート
の製造〕
実施例１で得た２−（６’ −アセトアニリノヘキサ１
／、 ３／、 ５／ −トリエニル）−１，３，３−ト
リメチル−５−クロロインドレニウムバークロレート４
．６ｇ、１−プロピル−２，３，３−トリメチルインド
レニウムバークロレート（融点１６４〜１６６℃）３．
０２ｇ、酢酸ナトリウム０．８２ｇとローブタノール５
０ｃｃを９０〜１００℃で１．５時間反応させた６冷却
後、析出した結晶を水洗して、熱メタノールで洗浄した
。収ｉ１．９８ｇ、融点１７５〜１７７℃、エタノール
中の極大吸収波長４８ｎｍ
実施例４
（１，３，３−トリメチル−５−クロロインド−１１−
プロピル−３Ｌ、３１−ジメチル−５′−クロロインド
−２＝２′ −へブタメチンシアニンバークロレート
の製造〕
実施例１で得た２−（６’ −アセトアニリノヘキサ−
１’、３’、５’ −トリエニル）−１，３，３−トリ
メチル−５−クロロインドレニウムバークロレート４．
６ｇ、１−プロピル−２，３，３−トリメチル−５−ク
ロロインドレニウムバークロレート（融点１９７〜１９
９℃）３．４ｇ、酢酸ナトリウム０．８２ｇとｎ−ブタ
ノール５０ｃｃを９０〜１００℃で１時間反応させた。Example 2 (1,3,3-trimethyl-5-chloroindo-11-
Ethyl-3', 3'-dimethyl-5'-chloroindo-2: Production of 2'-hebutamethine cyanine verchlorate] 2-(6'-acetanilinohexa- obtained in Example 1)
1',3',5'-trienyl)-1,3,3-trimethyl-5-chloroindolenium verchlorate4.
6g, 1-ethyl-2,3,3-trimethyl-5-chloroindolenium ethylsulfonate (wA point 165~
166℃) 3.2g, sodium acetate 0.82g and n-
50 cc of butanol was reacted at 90 to 100°C for 1.5 hours. After cooling, the precipitated crystals were collected by filtration and washed with hot methanol. Yield 3.07g, melting point 225-226℃,
Maximum absorption wavelength in ethanol 7520 m0 Example 3 (1,3,3-trimethyl-5-chloroindo-1'-
Propyl-3', 3'-dimethylindo-2=2'
-Production of hebutamethine cyanine verchlorate] 2-(6'-acetanilinohexa1 obtained in Example 1)
/, 3/, 5/ -trienyl)-1,3,3-trimethyl-5-chloroindolenium verchlorate 4
．． 6g, 1-propyl-2,3,3-trimethylindolenium verchlorate (melting point 164-166°C)3.
02g, sodium acetate 0.82g and lobetanol 5
After cooling, the precipitated crystals were washed with water and then with hot methanol. Yield: 1.98 g, melting point: 175-177°C, maximum absorption wavelength in ethanol: 48 nm Example 4 (1,3,3-trimethyl-5-chloroindo-11-
Production of propyl-3L, 31-dimethyl-5'-chloroindo-2=2'-hebutamethine cyanine verchlorate] 2-(6'-acetanilinohexa-obtained in Example 1)
1',3',5'-trienyl)-1,3,3-trimethyl-5-chloroindolenium verchlorate4.
6 g, 1-propyl-2,3,3-trimethyl-5-chloroindolenium verchlorate (melting point 197-19
9°C), 0.82g of sodium acetate, and 50cc of n-butanol were reacted at 90 to 100°C for 1 hour.
冷却後析出した結晶を濾取し、水洗後、熱メタノールで
洗浄した。After cooling, the precipitated crystals were collected by filtration, washed with water, and then washed with hot methanol.
収量３．１ｇ、融点２１９〜２２１℃、エタノール中の
極大吸収波長７５４ｎｍ。Yield: 3.1 g, melting point: 219-221°C, maximum absorption wavelength in ethanol: 754 nm.
実施例５
〔１−エチル−３，３−ジメチル−５−クロロインド−
１’ −エチル−３５３′ −ジメチルインド−２：２
′−へブタメチンシアニンバークロレートの製造〕
原料の１つである２−（６’ −アセトアニリノヘキサ
−１’、 ３’、 ５− トリエニル）−１−エチル−
３，３−ジメチルインドレニウムバークロレート
は次のように合成した。Example 5 [1-ethyl-3,3-dimethyl-5-chloroindo-
1'-ethyl-353'-dimethylindo-2:2
Production of '-hebutamethine cyanine verchlorate] One of the raw materials, 2-(6'-acetanilinohexa-1', 3', 5-trienyl)-1-ethyl-
3,3-dimethylindolenium verchlorate was synthesized as follows.
■−エチルー２．３．３− トリメチルインドレニウム
バークロレート８．８ｇ、■−アニリノー５−アニリノ
ベンター１，３−ジエン塩酸塩９．１ｇ、酢酸ナトリウ
ム２．６ｇと無水酢ａ１００ｃｃを９０〜１００℃で１
時間反応させた。冷却後、析出した結晶を濾取し、水洗
後メタノール、クロロホルムまたはアセトンで数回洗浄
した。収量９．１ｇ、融点２１８〜２１９℃。■-Ethyl-2.3.3-Trimethylindolenium barchlorate 8.8g, ■-anilino 5-anilinobenter 1,3-diene hydrochloride 9.1g, sodium acetate 2.6g and anhydrous vinegar A 100cc in 90-100 g. 1 in °C
Allowed time to react. After cooling, the precipitated crystals were collected by filtration, washed with water, and then washed several times with methanol, chloroform, or acetone. Yield: 9.1 g, melting point: 218-219°C.
上記で得た２−（６’ −アセトアニリノヘキサ−１’
、 ３’、 ５’ −トリエニル）−１−エチル−３，
３−ジメチル−５−クロロインドレニウムバークロレー
ト４゜４ｇ、■−エチルー２．３．３−トリメチル−５
−クロロインドレニウムエチルスルホネート３．２ｇ、
酢酸ナトリウム０．８２ｇとｎ−ブタノール５０ｃｃを
９０〜１００℃で１．５時間反応させた。冷却後、祈出
した結晶を濾取し、水洗後熱メタノールで洗浄した。収
量３．２ｇ、融、ｌｆｉ ２２１〜２２２℃、エタノー
ル中の極太吸収波長７４８ｒ＋ｍ。2-(6'-acetanilinohexa-1' obtained above)
, 3', 5'-trienyl)-1-ethyl-3,
3-dimethyl-5-chloroindolenium verchlorate 4°4g, ■-ethyl-2.3.3-trimethyl-5
- 3.2 g of chloroindolenium ethyl sulfonate,
0.82 g of sodium acetate and 50 cc of n-butanol were reacted at 90 to 100°C for 1.5 hours. After cooling, the crystals were collected by filtration, washed with water, and then washed with hot methanol. Yield 3.2g, melted, lfi 221-222°C, thick absorption wavelength in ethanol 748r+m.
実施例６
〔ｌ−エチル−３，３−ジメチルインド−１’、３’、
３’−トリメチルインド−２＝２′ −へブタメチンシ
アニンバークロレート
とＩＩ、ＣＩら
の製造〕
実施例５で得た２−（６’ −アセトアニリノヘキサ−
１’、 ３’、５’ −トリエニル）−１−エチル−３
，３−ジメチルインドレニウムバークロレート４．４ｇ
、 １，２゜３．３−テトラメチルインドレニウムバー
クロレート（融点２０３〜２０４℃）２．７ｇ、酢酸ナ
トリウム０．８２ｇとｎ−ブタノール５０ｃｃを９０〜
１００℃で１．５時間反応させた。冷却後析出した結晶
を濾取し、水洗後熱メタノールで洗浄した。収量１．９
ｇ、 ＠点１７１〜１７３℃、エタノール中の極太吸収
波長７４５ｎｍ。Example 6 [l-ethyl-3,3-dimethylindo-1',3',
3'-trimethylindo-2=2'-hebutamethine cyanine verchlorate and production of II, CI et al.] 2-(6'-acetanilinohexa- obtained in Example 5)
1', 3', 5'-trienyl)-1-ethyl-3
, 3-dimethylindolenium verchlorate 4.4g
, 2.7 g of 1,2゜3.3-tetramethylindolenium verchlorate (melting point 203-204°C), 0.82 g of sodium acetate and 50 cc of n-butanol in 90~
The reaction was carried out at 100°C for 1.5 hours. After cooling, the precipitated crystals were collected by filtration, washed with water, and then washed with hot methanol. Yield 1.9
g, @ point 171-173°C, ultra-thick absorption wavelength 745 nm in ethanol.
実施例７
〔１−プロピル−３，３−ジメチルインド−１′ −プ
ロピル−３′、３１−ジメチル−５−クロロインド−２
＝２′−へブタメチンシアニンバークロレートの製造〕
原料の１つである２−（６’ −アセトアニリノヘキサ
−１’、 ３’、 ５’ −トリエニル）１−プロピル
−３，３−ジメチルインドレニウムバークロレートＣ２
Ｈ９
は、次のように合成した。Example 7 [1-propyl-3,3-dimethylindo-1'-propyl-3',31-dimethyl-5-chloroindo-2
= Production of 2'-hebutamethine cyanine verchlorate] 2-(6'-acetanilinohexa-1', 3', 5'-trienyl)1-propyl-3,3-dimethyl, which is one of the raw materials Indolenium barchlorate C2
H9 was synthesized as follows.
１−プロピル−２，３，３−トリメチルインドレニウム
バークロレート２１．１ｇ、１−アニリノ−５−アニリ
ノペンタ−１，３−ジエン塩酸塩２０．９ｇ、酢酸ナト
リウＡ６．０ｇと無水酢Ｎ１２００ｃｃを９０〜１１０
℃で１．５時間反応した。冷却後、析出した結晶を濾取
し、水洗後、メタノール、クロロホルム又はアセトンで
数回洗浄した。収量１１．２ｇ、融点２１２〜２１３℃
。90 ~ 21.1 g of 1-propyl-2,3,3-trimethylindolenium verchlorate, 20.9 g of 1-anilino-5-anilinopenta-1,3-diene hydrochloride, 6.0 g of sodium acetate A, and 1200 cc of anhydrous vinegar N. 110
The reaction was carried out at ℃ for 1.5 hours. After cooling, the precipitated crystals were collected by filtration, washed with water, and then washed several times with methanol, chloroform, or acetone. Yield 11.2g, melting point 212-213℃
.
上記で得た２−（６’ −アセトアニリノヘキサ−１’
、３’、５’ −）−リエニル）−１−プロピル−３，
３−ジメチル−５−クロロインドレニウムバークロレー
ト４．６ｇ、 １−プロピル−２，３，３−トリメチル
−５−クロロインドレニウムバークロレート３．４ｇ、
酢酸ナトリウム０．８２ｇとｎ−ブタノール５０ｃｃを
９０−１００℃で１．５時間反応させた。冷却後、祈出
した結晶を濾取し、水洗後熱メタノールで洗浄した。収
量１．７ｇ、融点１７６〜１７８℃、エタノール中の極
大吸収波長７５１ｎｍ。2-(6'-acetanilinohexa-1' obtained above)
,3',5'-)-lienyl)-1-propyl-3,
4.6 g of 3-dimethyl-5-chloroindolenium verchlorate, 3.4 g of 1-propyl-2,3,3-trimethyl-5-chloroindolenium verchlorate,
0.82 g of sodium acetate and 50 cc of n-butanol were reacted at 90-100°C for 1.5 hours. After cooling, the crystals were collected by filtration, washed with water, and then washed with hot methanol. Yield: 1.7 g, melting point: 176-178°C, maximum absorption wavelength in ethanol: 751 nm.
実施例８
１−プロピル−３，３−ジメチル−１′−エチル−３′
３′−ジメチル−５−クロロインド−２：２’−ヘプタ
メチンシアニンバークロレート
とＨ７と１１５
の製造〕
実施例７で得た２−（６’ −アセトアニリノヘキサ−
１’ ３’ ５’ −トリエニル）−１−プロピル−３
，３−ジメチルインドレニウムバークロレート４．６ｇ
、１−エチル−２，３，３−トリメチル−５−クロロイ
ンドレニウムエチルスルホネート３．２ｇ、酢酸ナトリ
ウム０．８２ｇとｎ−ブタノール５０ｃｃを９０〜１０
０℃で１．５時間反応させた。冷却後、析出した結晶を
濾取し。Example 8 1-propyl-3,3-dimethyl-1'-ethyl-3'
3'-dimethyl-5-chloroindo-2: 2'-heptamethine cyanine verchlorate and production of H7 and 115] 2-(6'-acetanilinohexa- obtained in Example 7)
1'3'5' -trienyl)-1-propyl-3
, 3-dimethylindolenium verchlorate 4.6g
, 3.2 g of 1-ethyl-2,3,3-trimethyl-5-chloroindolenium ethyl sulfonate, 0.82 g of sodium acetate and 50 cc of n-butanol at 90-10 g
The reaction was carried out at 0°C for 1.5 hours. After cooling, the precipitated crystals were collected by filtration.
水洗後、熱メタノールで洗浄した。収量２．４ｇ、融点
２００〜２０２°Ｃ，エタノール中の極大吸収波長７５
Ｑｎｍ。After washing with water, it was washed with hot methanol. Yield 2.4g, melting point 200-202°C, maximum absorption wavelength in ethanol 75
Qnm.
次に本発明のシアニン色素が光学的情報記録媒体の材料
として優れていることを具体的に示すため、以下に応用
例を説明する。Next, in order to specifically demonstrate that the cyanine dye of the present invention is excellent as a material for optical information recording media, application examples will be described below.
応用例１
実施例１のシアニン色素をメタノールに溶解して１重量
％の溶液とした。その溶液をアクリル基版上にスピナー
塗布させて、乾燥させて厚さ４５０人の記録層を得た。Application Example 1 The cyanine dye of Example 1 was dissolved in methanol to make a 1% by weight solution. The solution was spin-coated onto an acrylic base plate and dried to obtain a recording layer with a thickness of 450 mm.
これらの記録媒体に波長７９０ｎｍの半導体レーザーを
用い、ビーム径１．５４ ｐ ｍに線速り、２ｍ／ｓｅ
ｃで０．７ＭＩ＋ｚの信号を記録した。この記録部に微
弱なレーザー光をあて信号を再生したところ、Ｃ／Ｎの
初期値５５ｄＢであった。次にこの記録媒体を７０℃の
オーブン中で４０日間放置した後、再び信号を再生した
ところ、Ｃ／Ｎ値は５０ｄＢであった。A semiconductor laser with a wavelength of 790 nm was used for these recording media, and a beam diameter of 1.54 pm and a linear velocity of 2 m/sec were used.
A signal of 0.7MI+z was recorded at c. When the signal was reproduced by applying a weak laser beam to this recording section, the initial value of C/N was 55 dB. Next, this recording medium was left in an oven at 70° C. for 40 days, and when the signal was reproduced again, the C/N value was 50 dB.
応用例２
実施例４のシアニン色素を１，２−ジクロロエタンに溶
解して、以降は応用例１と同様に実験した。Ｃ／Ｎの初
期値は５６ｄＢ、保存試験後のＣハ値は４９ｄＢであっ
た。Application Example 2 The cyanine dye of Example 4 was dissolved in 1,2-dichloroethane, and the experiment was carried out in the same manner as in Application Example 1. The initial value of C/N was 56 dB, and the C value after the storage test was 49 dB.
応用例３
実施例８のシアニン色素をメタノールに溶解して、以降
は応用例１と同様に実験した。Ｃハの初期値は５６ｄＢ
、保存試験後のＣハ値は５０ｄＢであった。Application Example 3 The cyanine dye of Example 8 was dissolved in methanol, and the experiment was carried out in the same manner as in Application Example 1. The initial value of C is 56dB
The C value after the storage test was 50 dB.
以上のように本発明のシアニン色素は、光学的情報記録
媒体の材料として従来の色素に比へて大幅に特性が優れ
、また工業的に多くの利点を有するものである。As described above, the cyanine dye of the present invention has significantly superior properties as a material for optical information recording media compared to conventional dyes, and has many industrial advantages.
Claims (1)
し、Ｒ＿３とＲ＿４はメチル基、エチル基又はプロピル
基を表わし、Ｘ＾■は酸陰イオンを表わす。但し、Ｒ＿
１とＲ＿２が等しく、かつＲ＿３とＲ＿４が等しい場合
は除く。） で表わされるシアニン色素。(1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 represent hydrogen atoms or chlorine atoms, and R_3 and R_4 represent methyl, ethyl, or propyl groups. In the expression, X^■ represents an acid anion. However, R_
Except when 1 and R_2 are equal and R_3 and R_4 are equal. ) A cyanine dye represented by
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61125110A JPS62280263A (en) | 1986-05-29 | 1986-05-29 | Cyanine dye |
| US07/031,374 US4847385A (en) | 1986-03-28 | 1987-03-30 | Cyanine dyes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61125110A JPS62280263A (en) | 1986-05-29 | 1986-05-29 | Cyanine dye |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62280263A true JPS62280263A (en) | 1987-12-05 |
Family
ID=14902094
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61125110A Pending JPS62280263A (en) | 1986-03-28 | 1986-05-29 | Cyanine dye |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62280263A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0321923A2 (en) * | 1987-12-21 | 1989-06-28 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Infrared absorbing cyanine dyes for dye-donor element used in laser-induced thermal dye transfer |
| WO1990002777A1 (en) * | 1988-09-09 | 1990-03-22 | Asahi Chemical Co., Ltd. | Cyanine compounds |
| JPH02106395A (en) * | 1988-08-31 | 1990-04-18 | Eastman Kodak Co | Fluorescent diphenyl ethylene capable of being thermally transferred |
-
1986
- 1986-05-29 JP JP61125110A patent/JPS62280263A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0321923A2 (en) * | 1987-12-21 | 1989-06-28 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Infrared absorbing cyanine dyes for dye-donor element used in laser-induced thermal dye transfer |
| JPH022074A (en) * | 1987-12-21 | 1990-01-08 | Eastman Kodak Co | Dye dative body element for laser induced thermal transfer containing infrared absorptive cyanine dye |
| JPH0517037B2 (en) * | 1987-12-21 | 1993-03-08 | Eastman Kodak Co | |
| JPH02106395A (en) * | 1988-08-31 | 1990-04-18 | Eastman Kodak Co | Fluorescent diphenyl ethylene capable of being thermally transferred |
| JPH053986B2 (en) * | 1988-08-31 | 1993-01-19 | Eastman Kodak Co | |
| WO1990002777A1 (en) * | 1988-09-09 | 1990-03-22 | Asahi Chemical Co., Ltd. | Cyanine compounds |
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